Surface-treated superabsorbent polymer particles

ABSTRACT

Surface-treated superabsorbent polymer particles obtained by mixing 100 parts by weight of superabsorbent polymer particles with 0.001 to 10 parts by weight of a hydroxyalkylamide, and heating the surface-treated superabsorbent polymer particles to crosslink molecular chains existing at least in the vicinity of the surfaces of the superabsorbent polymer particles is disclosed. Surface crosslinking the superabsorbent polymer particles with a hydroxyalkylamide substantially increases both the rate of liquid absorption and the quantity of liquid absorbed and retained by the superabsorbent particles.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a continuation-in-part of U.S. patent application Ser. No.09/390,462, filed Sep. 7, 1999, now U.S. Pat. No. 6,239,230.

FIELD OF THE INVENTION

The present invention relates to surface-crosslinked superabsorbentpolymer particles, and to methods of producing the surface-crosslinkedsuperabsorbent particles. The present invention also relates to the useof the surface-crosslinked particles in articles, such as diapers,catamenial devices, and wound dressings. More particularly, the presentinvention relates to surface treating superabsorbent polymer (SAP)particles, such as a neutralized, crosslinked, homopolymer or copolymerof acrylic acid, with a hydroxyalkylamide to substantially improve thewater absorption and water retention properties of the SAP particles.

BACKGROUND OF THE INVENTION

Water-absorbing resins are widely used in sanitary goods, hygienicgoods, wiping cloths, water-retaining agents, dehydrating agents, sludgecoagulants, disposable towels and bath mats, disposable door mats,thickening agents, disposable litter mats for pets,condensation-preventing agents, and release control agents for variouschemicals. Water-absorbing resins are available in a variety of chemicalforms, including substituted and unsubstituted natural and syntheticpolymers, such as hydrolysis products of starch acrylonitrile graftpolymers, carboxymethylcellulose, crosslinked polyacrylates, sulfonatedpolystyrenes, hydrolyzed polyacrylamides, polyvinyl alcohols,polyethylene oxides, polyvinylpyrrolidones, and polyacrylonitriles.

Such water-absorbing resins are termed “superabsorbent polymers,” orSAPs, and typically are lightly crosslinked hydrophilic polymers. SAPsare generally discussed in Goldman et al. U.S. Pat. Nos. 5,669,894 and5,599,335, the disclosures of which are incorporated herein byreference. SAPs can differ in their chemical identity, but all SAPs arecapable of absorbing and retaining amounts of aqueous fluids equivalentto many times their own weight, even under moderate pressure. Forexample, SAPs can absorb one hundred times their own weight, or more, ofdistilled water. The ability to absorb aqueous fluids under a confiningpressure is an important requirements for an SAP used in a hygienicarticle, such as a diaper.

As used here and hereafter, the term “SAP particles” refers tosuperabsorbent polymer particles in the dry state, i.e., particlescontaining from no water up to an amount of water less than the weightof the particles. The term “particles” refers to granules, fibers,flakes, spheres, powders, platelets, and other shapes and forms known topersons skilled in the art of superabsorbent polymers. The terms “SAPgel” and “SAP hydrogel” refer to a superabsorbent polymer in thehydrated state, i.e., particles that have absorbed at least their weightin water, and typically several times their weight in water. The terms“surface-treated SAP particle” and “surface-crosslinked SAP particle”refer to an SAP particle having its molecular chains present in thevicinity of the particle surface crosslinked by a compound applied tothe surface of the particle. The term “surface crosslinking” means thatthe level of functional crosslinks in the SAP particle in the vicinityof the surface of the particle is generally higher than the level offunctional crosslinks in the SAP particle in the interior of theparticle.

SAP particles can differ in ease and cost of manufacture, chemicalidentity, physical properties, rate of water absorption, and degree ofwater absorption and retention, thus making the ideal water-absorbentresin a difficult composition to design. For example, the hydrolysisproducts of starch-acrylonitrile graft polymers have a comparativelyhigh ability to absorb water, but require a cumbersome process forproduction and have the disadvantages of low heat resistance and decayor decomposition due to the presence of starch. Conversely, otherwater-absorbent polymers are easily and cheaply manufactured and are notsubject to decomposition, but do not absorb liquids as well as thestarch-acrylonitrile graft polymers.

Therefore, it would be extremely advantageous to provide a method ofincreasing the water absorption properties of a stable, easy tomanufacture SAP particles to match the superior water absorptionproperties of a difficult to manufacture particle. Likewise, it would beadvantageous to further increase the liquid absorption properties ofalready superior SAP particles.

In addition, conventional SAP particles all have a serious defect inthat their rates of liquid absorption are lower than fluff pulp andpaper. For example, when urine is excreted on a disposable diapercontaining conventional SAP particles, the urine can remain in contactwith the skin for a relatively long time and make the weareruncomfortable. This is attributed to the low rate at which the diapercan absorb urine.

Attempts have been made to increase the liquid absorption rate byincreasing the surface area of the SAP particle, i.e., by decreasing itsparticle size. However, when the particle size of the SAP particle isdecreased, it generally forms a “fish eye” upon contact with urine,which retards the speed of liquid absorption. When the SAP particles arein the form of granules, each granule constitutes a “fish eye” and thespeed of liquid absorption decreases. SAP particles in flake formexhibit a moderate increase in the speed of liquid absorption. But, SAPflakes are bulky and are difficult to transport and store.

Initially, the swelling capacity of an SAP particle on contact withliquids, also referred to as free swelling capacity, was the main factorin the design and development of SAP particles. Later, however, it wasfound that not only is the amount of absorbed liquid important, but thestability of the swollen gel, or gel strength, also important. The freeswelling capacity, on one hand, and the gel strength, on the other hand,represent contrary properties. Accordingly, SAP particles having aparticularly high absorbency typically exhibit a poor gel strength, suchthat the gel deforms under pressure (e.g., the load of a body), andprevents further liquid distribution and absorption.

A balanced relation between absorptivity (gel volume) and gel strengthis desired to provide proper liquid absorption, liquid transport, anddryness of the diaper and the skin when using SAP particles in a diaper.In this regard, not only is the ability of the SAP particle to retain aliquid under subsequent pressure an important property, but absorptionof a liquid against a simultaneously acting pressure, i.e., duringliquid absorption also is important. This is the case in practice when achild or adult sits or lies on a sanitary article, or when shear forcesare acting on the sanitary article, e.g., leg movements. This absorptionproperty is referred to as absorption under load.

Currently, there is a trend to reduce the size and thickness of sanitaryarticles for esthetic and environmental reasons (e.g., reduction ofwaste in landfills). This is accomplished by reducing the large volumeof fluff pulp and paper in diapers, and increasing the amount of SAPparticles. The SAP particles, therefore, have to perform additionalfunctions with respect to liquid absorption and transport whichpreviously were performed by the fluff pulp and paper, and which couldnot be accomplished satisfactorily with conventional SAP particles.

Investigators have researched various methods of improving the amount ofliquid absorbed and retained by SAP particles, especially under load,and the rate at which the liquid is absorbed. One preferred method ofimproving the absorption and retention properties of SAP particles is tosurface treat the SAP particles.

The surface treatment of SAP particles is well known. For example, U.S.Pat. No. 4,043,952 discloses the use of polyvalent metal compounds assurface treating compounds. U.S. Pat. No. 4,051,086 discloses the use ofglyoxal as a surface treatment to improve the absorption rate of SAPparticles. The surface treatment of SAP particles with crosslinkingagents having two or more functional groups capable of reacting withpendant carboxylate or other groups contained on the polymer comprisingthe SAP particle is disclosed in various patents. The surface treatmentimproves absorbency and gel rigidity to improve liquid flowability andprevent SAP particle agglomeration, as well as improving gel strength.

As disclosed in the art, the SAP particles are either mixed with thesurface-crosslinking agent optionally using small amounts of waterand/or an organic solvent, or an SAP hydrogel containing 10% to 40%, byweight, water is dispersed in a hydrophilic or hydrophobic solvent andmixed with the surface-crosslinking agent.

Prior surface crosslinking agents include diglycidyl ethers, halo epoxycompounds, polyols, polyamines, polyisocyanates, polyfunctionalaziridine compounds, and di- or tri-alkylhalides. Regardless of theidentity of the surface crosslinking agent, the agent used for thesurface treatment has at least two functional groups, and the SAPparticles are heated after the surface crosslinking agent is applied tothe surface of the SAP particles.

Surface-crosslinked SAP particles, in general, exhibit higher liquidabsorption and retention values than SAP particles having a comparablelevel of internal crosslinks, but lacking surface crosslinking. Internalcrosslinks arise from polymerization of the monomers comprising the SAPparticles, and are present in the polymer backbone. It has beentheorized that surface crosslinking increases the resistance of SAPparticles to deformation, thus reducing the degree of contact betweensurfaces of neighboring SAP particles when the resulting hydrogel isdeformed under an external pressure. The degree to which absorption andretention values are enhanced by surface crosslinking is related to therelative amount and distribution of internal and surface crosslinks, andto the particular surface crosslinking agent and method of surfacecrosslinking.

As understood in the art, surface-crosslinked SAP particles have ahigher level of crosslinking in the vicinity of the surface than in theinterior. As used herein, “surface” describes the outer-facingboundaries of the particle. For porous SAP particles, exposed internalsurface also are included in the definition of surface.

Prior methods of performing surface crosslinking of SAP particles aredisclosed, for example, in Obayashi U.S. Pat. No. 4,541,871, WO92/16565, WO 93/05080, Alexander U.S. Pat. No. 4,824,901, Johnson U.S.Pat. No. 4,789,861, Makita U.S. Pat. No. 4,587,308, Tsubakimoto U.S.Pat. No. 4,734,478, Kimura et al. U.S. Pat. No. 5,164,459, DE 4,020,780,and EPO 509,708. Surface crosslinking of SAPs is generally discussed inF. L. Buchholz et al., ed., “Modern Superabsorbent Polymer Technology,”Wiley-VCH, New York, N.Y., pages 97-108 (1998).

A problem encountered in several prior compounds and methods used tosurface crosslink SAP particles is the relatively high temperaturerequired to form the surface crosslinks between the SAP and the surfacecrosslinking agent. Typically, temperatures in excess of 180° C. arerequired to form the surface crosslinks. At such temperatures, the SAPparticle has a tendency to degrade in color from white or off-white totan or brown. Such color degradation provides an SAP particle that isesthetically unacceptable to consumers. In addition, a high surfacecrosslinking temperature can increase the residual monomer content ofthe SAP particle, which can lead to adverse environmental and healtheffects, or can lead to rejection of the SAP particles for failing tomeet specifications.

The present invention is directed to surface-treated SAP particles thatovercome the disadvantages associated with prior surface crosslinkingagents and with prior surface crosslinked SAP particles.

SUMMARY OF THE INVENTION

The present invention is directed to surface-treated SAP particles andto a method of surface treating SAP particles with a sufficient amountof a hydroxyalkylamide (HAA) to substantially improve thewater-absorption and water retention properties of the SAP particles. Inparticular, the present invention is directed to applying an HAA to asurface of the SAP particle, then heating the surface-treated SAPparticles at about 90° C. to about 170° C. for about 60 to about 180minutes to form surface crosslinks on the SAP particles.

In accordance with the present invention, SAP particles possess improvedwater absorption and water retention properties as a result surfacetreatment with a hydroxyalkylamide. Treatment with an HAA is especiallyeffective when performed on polyacrylate salts, hydrolyzedpolyacrylamides, or other polymers having a plurality of pendentneutralized carboxyl groups.

Therefore, the present invention is directed to surface-treated SAPparticles having about 0.001 to about 10 parts by weight of an HAA per100 parts by weight of SAP particles, and applied to the surfaces of theSAP particles to crosslink the molecular chains existing at least in thevicinity of the surface of the SAP particles.

One aspect of the present invention is to provide such surface-treatedSAP particles, and to a method of manufacturing the surface-treated SAPparticles comprising applying a sufficient amount of an HAA to surfacesof the SAP particles and heating the surface-treated SAP particles at asufficient temperature for a sufficient time for the hydroxyalkylamideto react with pendent groups on a polymer comprising the SAP particle toform surface crosslinks on the SAP particle.

Another aspect of the present invention is to heat the surface-treatedSAP particles at about 100° C. to about 160° C. for about 90 to about150 minutes to form surface crosslinks on the SAP particles.

Yet another aspect of the present invention is to providesurface-treated SAP particles exhibiting a high retention capacity, highgel strength, and high absorbency under load. This aspect is achieved bysurface coating a particle-shaped SAP with about 0.001% to about 10% byweight of a hydroxyalkylamide and subsequently heating to about 90° C.to about 170° C.

Another aspect of the present invention is to provide an SAP particlehaving surface crosslinks provided by a hydroxyalkylamide having thestructure:

wherein A is a bond, hydrogen, or a monovalent or polyvalent organicradical selected from the group consisting of a saturated or unsaturatedalkyl radical containing 1 to 60 carbon atoms, aryl,tri-C₁₋₄alkyleneamino, and an unsaturated radical containing one or moreethylenic groups [>C═C<]; R¹, selected independently, are hydrogen,straight or branched chain C₁₋₅alkyl, or straight or branched chainC₁₋₅hydroxyalkyl; R², selected independently, are radicals selected fromthe group consisting of hydrogen and straight or branched chainC₁₋₅alkyl, or the R² radicals can be joined to form, together with thecarbon atoms, a cycloalkyl ring; p and p′, independently, are integers 1to 4; n is an integer having a value of 1 or 2, and n′ is an integerhaving a value 0 to 2, or when n′ is 0, a polymer or copolymer (i.e., nhas a value greater than 1, preferably 2 to 10) formed from thehydroxyalkylamide when A is an unsaturated radical.

Another aspect of the present invention is to provide an SAP particlehaving surface crosslinks provided by a cyclic hydroxyalkylamide havingthe structure:

where R³ is a divalent radical selected from the group consisting of analkylene radical containing 1 to 4 carbon atoms and arylene.

Still another object of the present invention is to provide SAPparticles surface crosslinked with a hydroxyalkylamide in an amountsufficient to substantially improve the water absorbency and waterretention properties of the SAP particles, such as retention capacity,absorption rate, and gel strength, and to maintain a “dry feel” for theSAP particles after significant liquid absorption.

These and other aspects and advantages of the present invention willbecome apparent from the following detailed description of the preferredembodiments.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In accordance with the present invention, SAP particles are surfacetreated with a hydroxyalkylamide to substantially increase the rate ofliquid absorption, amount of liquid absorption, and overall retention ofliquids by the SAP particles. Surface-treatment of the SAP particles atany time after polymerization and sufficient drying to form solid SAPparticles improves liquid absorption properties. For economics and easeof manufacture, the surface treatment is most advantageously performedimmediately after the SAP particles are synthesized, dried to anappropriate water content, and sized, such as by grinding.

As will become apparent from the following detailed description of thepreferred embodiments, hydroxyalkylamide surface treatment substantiallyimproves the water absorption properties of SAP particles, which can beeither acidic or basic in nature. Of particular utility are SAPparticles containing a plurality of pendant, neutralized carboxyl groupsalong the polymer chain.

As stated above, the surface treatment of SAP particles is well known.However, many surface crosslinking agents exhibit disadvantages. Somesurface crosslinking agents have toxic properties and, therefore, cannotbe used in the sensitive field of hygiene because they pose a threat tohealth or the environment. For example, in addition to the risk of skinirritation, epoxy, glycidyl, isocyanate, and organic halogen compounds,have a sensitizing effect, and frequently have a carcinogenic andmutagenic potential. Polyamines are avoided as surface crosslinkingagents because of possible nitrosamine formation. In any case, when usedin diapers and other sanitary articles, residual amounts oftoxicologically critical crosslinking agents must be removed from theSAP particles, which involves additional process steps and increases thecost of the SAP particles.

In addition, a majority of the commonly used surface crosslinking agentsrequired heating at temperatures in excess of 180° C. in order to reactwith the SAP particles and form surface crosslinks. Heating at such ahigh temperature can increase the residual monomer content of thesurface crosslinked SAP particles. An increased residual monomer contentposes both toxicological and environmental concerns, and is unacceptablecommercially.

The high temperature required to form surface crosslinks also causes theSAP particles to degrade in color from white or off-white to tan orbrown. The tan to brown color of the SAP particles is estheticallyunacceptable to consumers, who equate the tan to brown color of the SAPparticles to an inferior product. The combination of color degradationand increased residual monomer can lead to SAP particles that do notmeet production specifications and, therefore, refused by the purchaserand/or consumer. The present invention overcomes these disadvantagesassociated with prior surface crosslinking agents by utilizing a HAA asthe surface crosslinking agent for the SAP particles.

The identity of the SAP particles utilized in the present invention isnot limited. The SAP particles are prepared by methods well known in theart, for example, solution or emulsion polymerization. The SAPparticles, therefore, can comprise an acidic water-absorbing resin, abasic water-absorbing resin, a blend of an acidic and basicwater-absorbing resin, or a multicomponent SAP particle as disclosed inWO 99/25393, the disclosure of which is incorporated herein byreference.

The SAP particles are prepared, for example, by:

(1) copolymerizing an acrylate salt and a crosslinking monomer inaqueous solution, and drying the resulting gel-like hydrous polymer byheating;

(2) dispersing an aqueous solution of acrylic acid and/or an alkalimetal acrylate, a water-soluble radical polymerization initiator, and acrosslinkable monomer in an alicyclic and/or an aliphatic hydrocarbonsolvent in the presence of a surface-active agent, and subjecting themixture to suspension polymerization;

(3) saponifying copolymers of vinyl esters and ethylenically unsaturatedcarboxylic acids or their derivatives;

(4) polymerizing starch and/or cellulose, a monomer having a carboxylgroup or capable of forming a carboxyl group upon hydrolysis, and acrosslinking monomer in an aqueous medium, and, as required, hydrolyzingthe resulting polymer; or

(5) reacting an alkaline substance with a maleic anhydride-typecopolymer containing maleic anhydride and at least one monomer selectedfrom α-olefins and vinyl compounds, and, as required, reacting thereaction product with a polyepoxy compound.

Other methods and monomers that provide SAP particles also are known inthe art.

Generally, acidic water-absorbing resins have carboxylate, sulfonate,sulfate, and/or phosphate groups incorporated along the polymer chain.Polymers containing these acid moieties are synthesized either frommonomers previously substituted with one or more of these acidicfunctional groups or by incorporating the acidic functional group intothe polymer after synthesis. To incorporate carboxyl groups into apolymer, any of a number of ethylenically unsaturated carboxylic acidscan be homopolymerized or copolymerized. Carboxyl groups also can beincorporated into the polymer chain indirectly by hydrolyzing ahomopolymer or copolymer of monomers such as acrylamide, acrylonitrile,methacrylamide, and alkyl acrylates or methacrylates.

An acidic water-absorbing resin present in an SAP particle can be eithera strong or a weak acidic water-absorbing resin. The acidicwater-absorbing resin can be a single resin, or a mixture of resins. Theacidic resin can be a homopolymer or a copolymer.

The acidic water-absorbing resin typically is a neutralized, lightlycrosslinked acrylic-type resin, such as neutralized, lightly crosslinkedpolyacrylic acid. The lightly crosslinked acidic resin typically isprepared by polymerizing an acidic monomer containing an acyl moiety,e.g., acrylic acid, or a moiety capable of providing an acid group,i.e., acrylonitrile, in the presence of a free radical crosslinker,i.e., a polyfunctional organic compound. The acidic resin can containother copolymerizable units, i.e., other monoethylenically unsaturatedcomonomers, well known in the art, as long as the polymer issubstantially, i.e., at least 10%, and preferably at least 25%, acidicmonomer units. To achieve the full advantage of the present invention,the acidic resin contains at least 50%, and more preferably, at least75%, and up to 100%, acidic monomer units. The acidic resin isneutralized at least 50 mole %, and preferably at least 70 mole %, witha base prior to surface crosslinking.

Ethylenically unsaturated carboxylic acid and carboxylic acid anhydridemonomers, and salts, useful in the acidic water-absorbing resin includeacrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid,α-cyanoacrylic acid, β-methylacrylic acid (crotonic acid),α-phenylacrylic acid, β-acryloxypropionic acid, sorbic acid,α-chlorosorbic acid, angelic acid, cinnamic acid, p-chlorocinnamic acid,β-stearylacrylic acid, itaconic acid, citraconic acid, mesaconic acid,glutaconic acid, aconitic acid, maleic acid, fumaric acid,tricarboxyethylene, 2-methyl-2-butene dicarboxylic acid, maleamic acid,N-phenyl maleamide, maleamide, maleic anhydride, fumaric anhydride,itaconic anhydride, citraconic anhydride, mesaconic anhydride, methylitaconic anhydride, ethyl maleic anhydride, diethylmaleate,methylmaleate, and maleic anhydride.

Sulfonate-containing acidic resins can be prepared from monomerscontaining functional groups hydrolyzable to the sulfonic acid form, forexample, alkenyl sulfonic acid compounds and sulfoalkylacrylatecompounds. Ethylenically unsaturated sulfonic acid monomers includealiphatic or aromatic vinyl sulfonic acids, such as vinylsulfonic acid,allyl sulfonic acid, vinyl toluene sulfonic acid, styrene sulfonic acid,acrylic and methacrylic sulfonic acids, such as sulfoethyl acrylate,sulfoethyl methacrylate, sulfopropyl acrylate, 2-vinyl-4-ethylbenzene,2-allylbenzene sulfonic acid, 1-phenylethylene sulfonic acid,sulfopropyl methacrylate, 2-hydroxy-3-methacryloxypropyl sulfonic acid,and 2-acrylamide-2-methylpropane sulfonic acid.

Sulfate-containing acidic resins are prepared by reacting homopolymersor copolymers containing hydroxyl groups or residual ethylenicunsaturation with sulfuric acid or sulfur trioxide. Examples of suchtreated polymers include sulfated polyvinylalcohol, sulfatedhydroxyethyl acrylate, and sulfated hydroxypropyl methacrylate.Phosphate-containing acidic resins are prepared by homopolymerizing orcopolymerizing ethylenically unsaturated monomers containing aphosphoric acid moiety, such as methacryloxy ethyl phosphate.

Copolymerizable monomers for introduction into the acidic resin, or intothe basic resin, include, but are not limited to, ethylene, propylene,isobutylene, C₁ to C₄ alkyl acrylates and methacrylates, vinyl acetate,methyl vinyl ether, and styrenic compounds having the formula:

wherein R represents hydrogen or a C₁₋₆ alkyl group, and wherein thephenyl ring optionally is substituted with one to four C₁₋₄ alkyl orhydroxy groups.

Suitable C₁ to C₄ alkyl acrylates include, but are not limited to,methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl acrylate,n-butyl acrylate, and the like, and mixtures thereof. Suitable C₁ to C₄alkyl methacrylates include, but are not limited to, methylmethacrylate, ethyl methacrylate, isopropyl methacrylate,n-propylmethylmethacrylate, -butyl methacrylate, and the like, andmixtures thereof or with C₁₋₄ alkyl acrylates. Suitable styreniccompounds include, but are not limited to, styrene, α-methylstyrene,p-methylstyrene, t-butyl styrene, and the like, and mixtures thereof orwith C₁₋₄ alkyl acrylates and/or methacrylates.

As set forth above, polymerization of acidic monomers, and optionalcopolymerizable monomers, most commonly is performed by free radicalprocesses in the presence of a polyfunctional organic compound. Theacidic resins are crosslinked to a sufficient extent such that thepolymer is water insoluble. Crosslinking renders the acidic resinssubstantially water insoluble, and, in part, serves to determine theabsorption capacity of the resins. For use in absorption applications,an acidic resin is lightly crosslinked, i.e., has a crosslinking densityof less than about 20%, preferably less than about 10%, and mostpreferably about 0.01% to about 7%.

A crosslinking agent most preferably is used in an amount of less thanabout 7 wt %, and typically about 0.1 wt % to about 5 wt %, based on thetotal weight of monomers. Examples of crosslinking polyvinyl monomersinclude, but are not limited to, polyacrylic (or polymethacrylic) acidesters represented by the following formula (I); and bisacrylamides,represented by the following formula (II).

wherein X is ethylene, propylene, trimethylene, cyclohexyl,hexamethylene, 2-hydroxypropylene, —(CH₂CH₂O)_(p)CH₂CH₂—, or

p and r are each an integer 5 to 40, and k is 1 or 2;

wherein 1 is 2 or 3.

The compounds of formula (I) are prepared by reacting polyols, such asethylene glycol, propylene glycol, trimethylolpropane, 1,6-hexanediol,glycerin, pentaerythritol, polyethylene glycol, or polypropylene glycol,with acrylic acid or methacrylic acid. The compounds of formula (II) areobtained by reacting polyalkylene polyamines, such as diethylenetriamineand triethylenetetramine, with acrylic acid.

Specific crosslinking monomers include, but are not limited to,1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butyleneglycol diacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycoldiacrylate, diethylene glycol dimethacrylate, ethoxylated bisphenol Adiacrylate, ethoxylated bisphenol A dimethacrylate, ethylene glycoldimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanedioldimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycoldiacrylate, polyethylene glycol dimethacrylate, triethylene glycoldiacrylate, triethylene glycol dimethacrylate, tripropylene glycoldiacrylate, tetraethylene glycol diacrylate, tetraethylene glycoldimethacrylate, dipentaerythritol pentaacrylate, pentaerythritoltetraacrylate, pentaerythritol triacrylate, trimethylolpropanetriacrylate, trimethylolpropane trimethacrylate,tris(2-hydroxyethyl)isocyanurate triacrylate,tris(2-hydroxyethy)isocyanurate trimethacrylate, divinyl esters of apolycarboxylic acid, diallyl esters or a polycarboxylic acid, triallylterephthalate, diallyl maleate, diallyl fumarate,hexamethylenebismaleimide, trivinyl trimellitate, divinyl adipate,diallyl succinate, a divinyl ether of ethylene glycol, cyclopentadienediacrylate, tetraallyl ammonium halides, or mixtures thereof. Compoundssuch as divinylbenzene and divinyl ether also can be used to crosslinkthe poly(dialkylaminoalkyl acrylamides). Especially preferredcrosslinking agents are N,N′-methylenebisacrylamide,N,N′-methylenebismethacrylamide, ethylene glycol dimethacrylate, andtrimethylolpropane triacrylate.

The acidic resin, either strongly acidic or weakly acidic, can be anyresin that acts as an SAP in its neutralized form. Examples of acidicresins include, but are not limited to, polyacrylic acid, hydrolyzedstarch-acrylonitrile graft copolymers, starch-acrylic acid graftcopolymers, saponified vinyl acetate-acrylic ester copolymers,hydrolyzed acrylonitrile copolymers, hydrolyzed acrylamide copolymers,ethylene-maleic anhydride copolymers, isobutylene-maleic anhydridecopolymers, poly(vinylsulfonic acid), poly(vinylphosphonic acid),poly(vinylphosphoric acid), poly(vinylsulfuric acid), sulfonatedpolystyrene, poly(aspartic acid), poly(lactic acid), and mixturesthereof. The preferred acidic resins are the polyacrylic acids.

The final acidic SAP particle contains from about 50 to 100 percentneutralized pendant carboxylate salt units. Accordingly, it may benecessary to neutralize carboxylic acid groups. Neutralization ofcarboxylic acid groups is accomplished using a strong organic orinorganic base, such as sodium hydroxide, potassium hydroxide, ammonia,ammonium hydroxide, or an organic amine.

The sequence and the number of reactions (e.g., polymerization,hydrolysis, and neutralization) performed to obtain the desired acidfunctionality attached to acidic resin backbone are not critical. Anynumber and sequence resulting in a final SAP particle which possesses 0to about 90 percent copolymerizable monomer units and about 10 to about100 percent monomer units having pendant acid groups, and neutralized atleast 50 mole %, is suitable.

Analogous to the acidic resin, a basic water-absorbing resin present inthe SAP particles can be a strong or weak basic water-absorbing resins.The basic water-absorbing resin can be a single resin or a mixture ofresins. The basic resin can be a homopolymer or a copolymer. Theidentity of the basic resin is not limited as long as the basic resin iscapable of reacting with a β-HAA. The strong basic resins typically arepresent in the hydroxide (OH) or bicarbonate (HCO₃) form.

The basic water-absorbing resin typically is a lightly crosslinkedacrylic-type resin, such as a poly(vinylamine). The basic resin also canbe a polymer such as a lightly crosslinked polyethylenimine, apoly(allylamine), a poly(allylguanidine), a poly(dimethyldiallylammoniumhydroxide), a quaternized polystyrene derivative, such as

a guanidine-modified polystyrene, such as

a quaternized poly((meth)acrylamide) or ester analog, such as

wherein Me is methyl, R₄ is hydrogen or methyl, n is a number 1 to 8,and q is a number from 10 to about 100,000, or a poly(vinylguanidine),i.e., poly(VG), a strong basic water-absorbing resin having the generalstructural formula (III)

wherein q is a number from 10 to about 100,000, and R₅ and R₆,independently, are selected from the group consisting of hydrogen, C₁-C₄alkyl, C₃-C₆ cycloalkyl, benzyl, phenyl, alkyl-substituted phenyl,naphthyl, and similar aliphatic and aromatic groups. The lightlycrosslinked basic water-absorbing resin can contain othercopolymerizable units and is crosslinked using a polyfunctional organiccompound, as set forth above with respect to the acidic water-absorbingresin.

A basic water-absorbing resin used in the present SAP particlestypically contains an amino or a guanidine group. Accordingly, awater-soluble basic resin can be crosslinked in solution by suspendingor dissolving an uncrosslinked basic resin in an aqueous or alcoholicmedium, then adding a di- or polyfunctional compound capable ofcrosslinking the basic resin by reaction with the amino groups of thebasic resin. Such crosslinking agents include, for example,multifunctional aldehydes (e.g., glutaraldehyde), multifunctionalacrylates (e.g., butanediol diacrylate, TMPTA), halohydrins (e.g.,epichlorohydrin), dihalides (e.g., dibromopropane), disulfonate esters(e.g., ZS(O₂)O—(CH₂)_(n)—OF(O)₂Z, wherein n is 1 to 10, and Z is methylor tosyl), multifunctional epoxies (e.g., ethylene glycol diglycidylether), multifunctional esters (e.g., dimethyl adipate), multifunctionalacid halides (e.g., oxalyl chloride), multifunctional carboxylic acids(e.g., succinic acid), carboxylic acid anhydrides (e.g., succinicanhydride), organic titanates (e.g., TYZOR A A from DuPont), melamineresins (e.g., CYMEL 301, CYMEL 303, CYMEL 370, and CYMEL 373 from CytecIndustries, Wayne, N.J.), hydroxymethyl ureas (e.g.,N,N′-dihydroxymethyl-4,5-dihydroxyethylene-urea), and multifunctionalisocyanates (e.g., toluene diisocyanate or methylene diisocyanate).Crosslinking agents for basic resins also are disclosed in Pinschmidt,Jr. et al. U.S. Pat. No. 5,085,787, incorporated herein by reference,and in EP 450 923.

Conventionally, the crosslinking agent is water or alcohol soluble, andpossesses sufficient reactivity with the basic resin such thatcrosslinking occurs in a controlled fashion, preferably at a temperatureof about 25° C. to about 150° C. Preferred crosslinking agents areethylene glycol diglycidyl ether (EGDGE), a water-soluble diglycidylether, and a dibromoalkane, an alcohol-soluble compound.

The basic resin, either strongly or weakly basic, therefore, can be anyresin that acts as an SAP in its charged form. Examples of basic resinsinclude a poly(vinylamine), a polyethylenimine, a poly(vinylguanidine),a poly(allylamine), a poly(allylguanidine), or a poly(dialkylaminoalkyl(meth)acrylamide) prepared by polymerizing and lightly crosslinking amonomer having the structure

or its ester analog

wherein R₇ and R₈, independently, are selected from the group consistingof hydrogen and methyl, Y is a divalent straight chain or branchedorganic radical having 1 to 8 carbon atoms, R₉ is hydrogen, and R₁₀ ishydrogen or an alkyl radical having 1 to 4 carbon atoms. Preferred basicresins include a poly(vinylamine), polyethylenimine,poly(vinylguanadine), poly(methylaminoethyl acrylamide), andpoly(methylaminopropyl methacrylamide).

There is no particular restriction on the shape of the SAP particlesused in this invention. The SAP particles can be in the form of spheresobtained by inverse phase suspension polymerization, flakes obtained bydrum drying, or irregularly shaped particles obtained by pulverizingsolid polymer. From the standpoint of the speed of absorption, the SAPparticles preferably are small, and typically the particle size is about20 to about 2000 μm, preferably about 50 about 850 μm.

The SAP particles, comprising an acidic resin, basic resin, a blend ofacidic and basic resin, or multicomponent SAP particles, are surfacetreated by applying a surface crosslinking agent to the surface of theSAP particles, followed by heating the particles. Surface treatmentresults in surface crosslinking of the SAP particles. It has been foundthat surface treating SAP particles with a β-hydroxyalkylamide enhancesthe ability of the SAP particles to absorb and retain aqueous mediaunder a load.

In general, surface crosslinking is achieved by contacting SAP particleswith a solution of an HAA to wet predominantly only the outer surfacesof the SAP particles. Surface crosslinking of the SAP particles then isperformed, preferably by heating at least the wetted surfaces of the SAPparticles.

The surface crosslinking agent utilized in the present invention is ahydroxyalkylamine. For example, HAAs are disclosed in Swift et al. U.S.Pat. No. 4,076,917, incorporated herein by reference. An HAA useful inthe present invention has the following formula:

wherein A is a bond, hydrogen, or a monovalent polyvalent organicradical selected from the group consisting of a saturated or unsaturatedalkyl radical contain 1 to 60 carbon atoms, such as methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, eicosyl,triacontyl, tetracontyl, pentacontyl, hexylcontyl, and the like, aryl,for example, mono- and dicyclic aryl, such as phenyl, naphthyl, and thelike, tri-C₁₋₄ alkyleneamine, such as trimethyleneamino,triethyleneamino, and the like, and an unsaturated radical containingone or more ethylenic groups [>C═C<], such as ethenyl, 1-methylethenyl,3-butenyl-1,3-diyl, 2-propenyl-1,2-diyl, carboxy C₁₋₄ alkenyl, such as3-carboxy-2-propenyl, and the like, C₁₋₄ alkoxy carbonyl lower alkenyl,such as 3-methoxycarbonyl-2-propenyl, and the like; R¹, selectedindependently, are hydrogen, straight or branched chain C₁₋₅ alkyl, suchas methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, pentyl, andthe like, or straight or branched chain C₁₋₅ hydroxyalkyl, such ashydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl,3-hydroxybutyl, 2-hydroxy-2-methylpropyl, 5-hydroxypentyl,4-hydroxypentyl, 3-hydroxypentyl, 2-hydroxypentyl, and the isomers ofpentyl; R², selected independently, are radicals selected from the groupconsisting of hydrogen and straight or branched C₁₋₅ alkyl, or the R²radicals can be joined to form, together with the carbon atoms, acycloalkyl ring, such as cyclopentyl, cyclohexyl, and the like; p andp′, independently, are an integer 1 to 4; n is an integer having a valueof 1 or 2, and n′ is an integer having a value of 0 to 2, or when n′ is0, a polymer or copolymer (i.e., n has a value greater than 1,preferably 2-10) formed from the β-hydroxyalkylamide when A is anunsaturated radical.

Preferred HAAs are wherein R¹ is H or C₁₋₅hydroxyalkyl, n and n′ areeach 1, —A— is —(CH₂)_(m)—, m is 0-8, preferably 2-8, each R² on theα-carbon is H, and one of the R² radicals on the beta carbon in eachcase is H and the other is H or a C₁₋₅ alkyl, and q and q′,independently, are an integer 1 to 3; that is,

Most preferred HAAs have the formula:

wherein both R² groups are H or both R² groups are —CH₃.

Specific examples of HAA compounds include, but are not limited to,bis[N,N-di(β-hydroxyethyl)]adipamide,bis[N,N-di(β-hydroxypropyl)]succinamide,bis[N,N-di(β-hydroxyethyl)]azelamide,bis[N-N-di(β-hydroxypropyl)]adipamide, andbis[N-methyl-N-(β-hydroxyethyl)]oxamide. A commercially available β-HAAis PRIMID™ XL-552 from EMS-CHEMIE, Dornat, Switzerland. PRIMID™ XL-522has the structure

Another commercially available HAA is PRIMID™ QM-1260 from EMS-CHEMIE,having the structure:

In another embodiment, the HAA has the cyclic structure

wherein R³ is a divalent radical selected from the group consisting ofan alkylene radical containing 1 to 4 carbon atoms and arylene. Inpreferred embodiments, R³, independently, is (CH₂)₂, (CH₂)₃, or

Additional HAA compounds are the N-substituted ethylhydroxy, methyl andethylhydroxy, and di(ethylhydroxy) derivatives of oxamide, malonamide,succinamide, glutaramide, adipamide, maleamide, a mixture of succinamideand glutaramide, and —(C═O)CH₂OCH₂C(═O)—. Such compounds include, butare not limited to, bis[N-methyl-N-(β-hydroxyethyl)]succinamide,bis[N-methyl-N-(β-hydroxyethyl)]glutaramide,bis[N-methyl-N-(β-hydroxyethyl)]succinamide/glutaramide,bis[N,N-(dihydroxyethyl)]succinamide,bis[N,N-(dihydroxyethyl)]glutaramide,bis[N,N-(dihydroxyethyl)]succinamide/glutaramide,bis[N,N-(dihydroxyethyl)]succinamide/glutaramide/adipamide,bis[N,N-(dihydroxyethyl)]glutaramide/adipamide, and other mixtures andsimilar compounds.

Typically, the SAP particles are surface treated using a solution of anHAA. The solution contains about 0.01% to about 4%, by weight, HAA, andpreferably about 0.4% to about 2%, by weight, HAA in a suitable solvent,for example, water, an alcohol, or a glycol. The solution can be appliedas a fine spray onto the surface of freely tumbling SAP particles at aratio of about 1:0.01 to about 1:0.5 parts by weight SAP particles tosolution of HAA.

To achieve the desired absorption properties, the HAA is distributedevenly on the surfaces of the SAP particles. For this purpose, mixing isperformed in suitable mixers, e.g., fluidized bed mixers, paddle mixers,a rotating disc mixer, a ribbon mixer, a screw mixer, milling rolls, ortwin-worm mixers.

The amount of HAA used to surface treat the SAP particles variesdepending upon the identity of SAP particles. Generally, the amount ofHAA used to surface treat the SAP particles in about 0.001 to about 10parts by weight per 100 parts by weight of the SAP particles. When theamount of HAA exceeds 10 parts by weight, the SAP particles are toohighly surface crosslinked, and the resulting SAP particles have areduced absorption capacity. On the other hand, when SAP particles aresurface crosslinked with less than 0.001 part by weight HAA, there is noobservable effect.

A preferred amount of HAA used to surface crosslink the SAP particles isabout 0.01 to about 5 parts by weight per 100 parts, by weight, SAPparticles. To achieve the full advantage of the present invention, theamount of HAA used as a surface crosslinking agent is about 0.05 toabout 1 part, by weight, per 100 weight parts of SAP particles.

The drying and surface crosslinking of the surface-treated SAP particlesare achieved by heating the surface-treated particles at a suitabletemperature, e.g., about 90° C. to about 170° C., and preferably about100° C. to about 165° C. To achieve the full advantage of the presentinvention, the surface-treated particles are heated at about 100° C. toabout 160° C. At this temperature, the SAP particles are surfacecrosslinked with the HAA without degrading the color of the SAPparticles and without increasing the residual monomer content of the SAPparticles.

The surface-treated SAP particles are heated for about 60 to about 180minutes, preferably about 60 to about 150 minutes, to effect surfacecrosslinking. To achieve the full advantage of the present invention,the SAP particles are heated for about 75 to about 120 minutes.

Ordinary dryers or heating ovens can be used for heating thesurface-treated SAP particles and the HAA. Such heating apparatusincludes, for example, an agitated trough dryer, a rotating dryer, arotating disc dryer, a kneading dryer, a fluidized bed dryer, apneumatic conveying dryer, and an infrared dryer. However, any othermethod of reacting the HAA with the polymer of the SAP particle toachieve surface crosslinking of the SAP particles, such as microwaveenergy, can be used. In the surface treating and surface crosslinkingsteps, the mixer can be used to perform simultaneous mixing and heatingof the HAA and SAP particles, if the mixer is of a type that can beheated.

As previously stated, surface treating with an HAA, and subsequent orsimultaneous heating, provides additional polymer crosslinks in thevicinity of the surface of the SAP particles. The gradation incrosslinking from the surface of the SAP particles to interior, i.e.,the anisotropy of crosslink density, can vary, both in depth andprofile. Thus, for example, the depth of surface crosslinking can beshallow, with a relatively sharp transition from a high level to a lowlevel of crosslinking. Alternatively, for example, the depth of surfacecrosslinking can be a significant fraction of the dimensions of the SAPparticle, with a broader transition.

Depending on size, shape, porosity, as well as functionalconsiderations, the degree and gradient of surface crosslinking can varywithin a given type of SAP particle. Depending on variations insurface:volume ratio within the SAP particles (e.g., between small andlarge particles), it is typical for the overall level of crosslinking tovary over the group of SAP particles (e.g., is greater for smallerparticles).

Surface crosslinking generally is performed after the final boundariesof the SAP particles are essentially established (e.g., by grinding,extruding, or foaming). However, it is also possible to effect surfacecrosslinking concurrently with the creation of final boundaries.Furthermore, some additional changes in SAP particle boundaries canoccur even after surface crosslinks are introduced.

The following examples illustrate the present surface crosslinked SAPparticles. It should be understood, however, that these examples aremerely illustrative, and that the scope of this invention is not limitedto these examples.

In the following examples, the SAP particles are lightly crosslinkedpolyacrylic acid polymers, neutralized about 75% to about 80% withsodium hydroxide. The sodium polyacrylate was made by methods well knownin the art.

EXAMPLE 1

A 2% to 50%, by weight, solution of PRIMID™ XL-552 in water was appliedto the surface of the SAP particles, at the rate of 3 to 7 grams of theHAA solution per 100 grams of SAP particles. The surface-treated SAPparticles then were heat treated at about 150° C. to about 170° C. forabout 60 to about 150 minutes. The best results were achieved using agreater than 10% PRIMID™ XL-552 solution applied at about 7 grams of HAAsolution per 100 grams of SAP particles, then heat treating for 135 to150 minutes at about 165° C. The performance results are summarized inTable 1.

EXAMPLE 2

A solution containing 1% to 5%, by weight, of PRIMID™ XL-552 and 0% to37.5%, by weight, propylene glycol in water was applied to the surfaceof SAP particles, at the rate of about 4 to about 10 grams of solutionper 100 grams of SAP particles. The surface-treated SAP particles thenwere heat treated at about 150° C. to about 170° C. for about 60 toabout 120 minutes. The best results were achieved using a 3.5% PRIMID™XL-552/25% propylene glycol solution applied at about 7 grams ofsolution per 100 grams of SAP particles, then heat treating for about120 minutes at 160° C. The performance results are summarized in Table1.

EXAMPLE 3

A solution containing 1% to 5%, by weight, PRIMID™ XL-552 and 0% to 25%,by weight, 1,3-butanediol in water was applied to the surface of SAPparticles, at the rate of about 4 to about 10 grams of solution per 100grams of SAP particles. The surface-treated SAP particles then were heattreated at about 150° C. to about 170° C. for about 60 to about 120minutes. The best results were achieved using a 3.5% PRIMID™ XL-552/25%1,3-butanediol solution applied at about 7 grams of solution per 100grams of SAP particles, then heat treating for about 120 minutes atabout 160° C. The performance results are summarized in Table 1.

EXAMPLE 4

A solution containing 1% to 5%, by weight, PRIMID™ XL-552 and 0 to 25%1,4-butanediol in water was applied to the surface of SAP particles, atthe rate of about 4 to about 10 grams of solution per 100 grams of SAPparticles. The surface-treated SAP particles then were heat treated atabout 150° C. to about 170° C. for about 60 to about 120 minutes. Thebest results were achieved using a 3.5% PRIMID™ XL-552/25%1,4-butanediol solution applied at about 7 grams of solution per 100grams of SAP particles, then heat treating for about 120 minutes at 160°C. The performance results are summarized in Table 1.

EXAMPLE 5

A solution containing 1% to 5%, by weight, PRIMID™ XL-552 and 0% to 25%,by weight, ethanol in water was applied to the surface of SAP particles,at the rate of about 4 to about 10 grams of solution per 100 grams ofSAP particles. The surface-treated SAP particles then were heat treatedat 150° C. to about 170° C. for about 60 to about 120 minutes. The bestresults were achieved using a 3.5% PRIMID™ XL-552/25% ethanol solutionapplied at about 7 grams of solution per 100 grams of polymer, then heattreating for about 120 minutes at 160° C. The performance results aresummarized in Table 1.

Examples 1-5 illustrate that the scope of cosolvents (e.g., ethanol) andadditional surface crosslinking agents (e.g., a diol) that can be usedin combination with the HAA is broad. Examples of cosolvents include,but are not limited to, alcohols, e.g., methanol, ethanol, andisopropanol, and ketones, e.g., acetone.

An additional surface crosslinking agent can be any compound that reactswith a pendant moiety of the polymer comprising the SAP particles, andthat inhibits the swell of SAP particles, can be used in conjunctionwith the HAA. Examples of additional surface crosslinking agentsinclude, but are not limited to, diols, triols, polyols, e.g., ethyleneglycol, propylene glycol, and 1,3-butanediol, and similarhydroxyl-containing compounds. Divalent and trivalent metal salts can beused as additional surface crosslinking agents, as swell suppressants.The HAA also can be used in combination with other surface crosslinkingagents, such as EGDGE, and especially with any other surfacecrosslinking compound that can react with the polymer comprising the SAPparticles at temperatures below 160° C.

The following Table 1 summarizes various specific surface crosslinkedSAP particles generally disclosed in Examples 1-5, and the adsorbentproperties exhibited by the surface crosslinked SAP particles. In thetest results set forth in Table 1, the surface-treated SAP particleswere tested for absorption under load at 0.7 psi (AUL (0.7 psi)).Absorption under load (AUL) is a measure of the ability of an SAP toabsorb fluid under an applied pressure. The AUL was determined by thefollowing method as disclosed in U.S. Pat. No. 5,149,335, incorporatedherein by reference.

An SAP (0.160 g+/−0.001 g) is carefully scattered onto a 140-micron,water-permeable mesh attached to the base of a hollow Plexiglas cylinderwith an internal diameter of 25 mm. The sample is covered with a 100 gcover plate and the cylinder assembly weighed. This gives an appliedpressure of 20 g/cm² (0.28 psi). Alternatively, the sample can becovered with a 250 g cover plate to give an applied pressure of 51 g/cm²(0.7 psi). The screened base of the cylinder is placed in a 100 mm petridish containing 25 milliliters of a test solution (usually 0.9% saline),and the polymer is allowed to absorb for 1 hour (or 3 hours). Byreweighing the cylinder assembly, the AUL (at a given pressure) iscalculated by dividing the weight of liquid absorbed by the dry weightof polymer before liquid contact.

The test results in Table 1 also set forth the centrifuge retentioncapacity (CRC) of the test samples. The centrifuge retention capacity ofan SAP is a measure of the absorptive capacity of the SAP. Inparticular, the CRC test is a method of determining the absorbentcapacity of an SAP in grams of 0.9% saline (NaCl) solution per gram ofpolymer. This test includes swelling the SAP in a “teabag” immersed in0.9% NaCl solution for 30 minutes, then centrifuged for three minutes.The ratio of retained liquid weight to initial weight of the dry SAP isthe absorptive capacity of the superabsorbent polymer, or the CRC.

The CRC test was performed as follows:

Apparatus

Electronic Balance, accuracy of 0.0001 gram

Plastic Tray, 44 cm×39 cm×10 cm

Heat sealer, T-bar plastic model

Teabag material (CH DEXTER), cut and sealed to produce a teabag 6.25×8.5cm

Weigh paper or plastic weighing boat

Timer

Centrifuge capable of 1400 rpm, 230 mm diameter

Tongs

Materials

SAP test sample

0.9% NaCl solution prepared with distilled or deionized water

Sample Preparation

(10 Samples Per Set Maximum 20 Samples Per 2000 ml NaCl Solution)

a) Pour approximately 2000 ml of NaCl solution into the tray. The liquidfilling height should be approximately ½ inch.

b) Fold teabag paper and seal two sides with heat sealer, leaving oneside open for polymer addition. Samples may be run in duplicate(optional).

c) Weight 0.2000+/−0.0050 grams polymer onto weigh paper or plasticweighing boat. Record weight and number.

d) Mark teabag with corresponding sample number. Transfer polymer toteabag and close open end with heat sealer.

e) Seal an empty teabag and mark it “blank.”

f) Set the timer for 30 minutes. Hold each teabag horizontally anddistribute the polymer evenly throughout the bag. Lay filled teabags andthe blank on the surface of the NaCl solution. Submerge each teabagusing a spatula to allow complete wetting. Start the timer.

Filled teabags were handled carefully with tongs, contacting only theedge of the teabag and not the area filled with polymer.

Centrifuge

a) After 20 minutes soak time, remove filled teabags and blank from NaClsolution. Position the teabags in the centrifuge with each bag stickingto the outer wall of the centrifuge basket.

b) Close the centrifuge lid. Set the timer for 3 minutes. Start thecentrifuge (ramp up quickly to 1400 rpm) and the timer at the same time.After 3 minutes, turn off the centrifuge (and apply the brake ifnecessary).

c) Weigh each filled teabag and blanks. Record weights.

Calculation${{CFC}\quad ( {g\text{/}g} )} = {\frac{\begin{matrix}{{{final}\quad {weight}\quad {of}\quad {teabag}} -} \\{{final}\quad {weight}\quad {of}\quad {blank}\text{-}{dry}\quad {polymer}\quad {weight}}\end{matrix}}{{dry}\quad {polymer}\quad {weight}}.}$

TABLE 1 Sam- 0.7 ple Coating¹⁾ CR³⁾ Temp.⁴⁾ Time⁵⁾ CRC⁶⁾ AUL  1 10%XL-552²⁾ 0.07 165° C. 150 min. 32.4 20.2 Soln⁸⁾  2 25% XL-552 Soln 0.07165° C. 135 min. 29.5 23.3  3 37.5% XL-552 Soln 0.07 165° C. 135 min.30.7 22.8  4 50% XL-552 Soln 0.07 165° C. 135 min. 30.4 22.1  5 5%XL-552/25% 0.07 165° C. 150 min. 31.5 26.2 Ethanol  6 3.5% XL-552/25%0.07 160° C. 120 min. 28.5 25.4 Propylene Glycol  7 3.5% XL-552/25% 0.07160° C. 120 min. 31.2 26.4 1,3-Butanediol  8 3.5% XL-552/25% 0.07 160°C. 120 min. 28 26.3 1,4-Butanediol  9⁷⁾ 25% Propylene 0.07 160° C. 120min. 33.0 10.4 Glycol Only 10⁷⁾ 25% 1,3-Butanediol 0.07 160° C. 120 min.33.6 10.4 Only 11⁷⁾ 25% 1,4-Butanediol 0.07 160° C. 120 min. 32.4 11.8Only ¹⁾Surface crosslinking composition; ²⁾XL-552 is PRIMID ™ XL-552;³⁾CR is a ratio of surface crosslinking composition applied to thesurface of the SAP particles, based on SAP weight; ⁴⁾Heatingtemperature; ⁵⁾Heating time; ⁶⁾CRC is retention capacity, in g 0.9% NaClper g of dry SAP; ⁷⁾Samples 9-11 are comparative examples; and ⁸⁾AllSamples 1-11 contain sufficient water to attain 100% solution weight.

The data in Table 1 shows that surface crosslinking using an HAAprovides surface-treated SAP particles having a greatly improved AUL(Samples 1-8) compared to SAP particles surface crosslinked only with adiol (Samples 9-11). In addition, an HAA surface crosslinker increasedthe AUL, without adversely affecting the CRC, which is both beneficialand unexpected in the art.

In another test, SAP particles were surface crosslinked with PRIMID™QM-1260. The results of this test, and the conditions used in thecrosslinking reaction and in the tests, are set forth in Table 2. TheSAP sample crosslinked with PRIMID™ QM-1260 (i.e., Sample 13) wascompared to an SAP sample crosslinked with an equal amount of PRIMID™XL-552 (Sample 12). Table 2 illustrates that an SAP crosslinking withPRIMID™ QM-1260 provides improved absorption properties (compare Sample13 to control Samples 9-11).

TABLE 2 Sample 0.7 # Coating¹⁾ CR³⁾ Temp⁴⁾ Time⁵⁾ CRC⁶⁾ AUL 12 4.9% wtXL-552, 0.06 160 120 min 28.5¹⁰⁾ 23.8 25% propylene glycol 13 4.9% wtQM-1260⁹⁾, 0.06 160 120 min 32.4 16.5 25% propylene glycol ⁹⁾QM-1260 isPRIMID ™ QM-1260; and ¹⁰⁾CRC of control SAP particles lacking surfacecrosslinks is 34.3.

The following Table 3 illustrates additional Examples 14-39 of SAPparticles surface crosslinked with various HAA compounds. The HAAcompounds listed in Table 3 have the following general structuralformula L—A—L. The individual L and A portions of the HAA compounds aredefined in Table 3.

The HAA compounds of Examples 14-39 were prepared by admixing a startingamine (e.g., diethanolamine) and a dimethyl ester of a dicarboxylicacid. No solvent is required, but can be added to the reaction mixtureif desired. The starting materials are liquids, therefore, the mixingstep is rapid. Optionally, catalytic amount of sodium hydroxide orpotassium hydroxide can be added to the reaction mixture. The reactionmixture then is heated to the reaction temperature (e.g., 120° C.).Methanol distills from the reaction mixture and is condensed. Thereaction time at this temperature is about 4 hours, and the reaction isessentially quantitative. The resulting HAA typically is a viscous amberliquid, but some HAAs can crystallize. A solvent, e.g., water orpropylene glycol, can be added to the reaction mixture prior to coolingto lower viscosity and prevent compound crystallization. No purificationstep is needed in the synthesis of an HAA.

In particular, the HAA compounds in the following table were preparedusing the following procedure. One molar equivalent of a carboxylic aciddiester and 1.24 mol % potassium hydroxide were added to a flask, andthe resulting mixture was stirred for 5 minutes under an argon blanket.A water aspirator was used to pull a vacuum of not less than 160 mm Hg.Two molar equivalents of an amine were added to the reaction flask, andthe reaction mixture was brought to the reaction temperature. Thereaction mixture then was maintained at the reaction temperature underan argon blanket for a sufficient time to complete the reaction. Analcohol was produced during the reaction, which was removed bydistillation as the reaction proceeded. After the reaction wascompleted, a solid HAA was recrystallized from a methanol/ethyl acetatesolution. Liquid HAAs typically were an oil which were heated at 50° C.under a high vacuum (<5 mm Hg) to remove residual starting materials.

Summary of Synthesis of HAAs Reaction Reaction Amine g Amine Ester gEster g KOH¹⁾ Time (hr.) Temp. (° C.) ethanolamine 28.050 diethylsuccinate 40.000 — 72 100 ethanolamine 30.5000 dimethyl glutarate 40.000— 17 100 ethanolamine 37.000 dimethyl malonate 40.000 — 2 20diethanolamine 131.000 dimethyl adipate 106.000 0.500 5.75 100diethanolamine 32.550 dimethyl malonate 20.000 0.145 4 100 ethanolamine24.675 dimethyl adipate 20.000 — 17 100 ethanolamine 29.400 diethyloxalate 20.000 — 17 20 ethanolamine 24.675 diethyl maleate 20.000 — 8100 2-(methylamino)ethanol 22.875 dimethyl malonate 20.000 — 9 1002-(methylamino)ethanol 21.552 diethyl succinate 25.000 0.134 5 1002-(methylamino)ethanol 18.750 dimethyl glutarate 20.000 0.100 — 100diethanolamine 28.767 diethyl oxalate 20.000 — 1.5 1002-(methylamino)ethanol 20.548 diethyl oxalate 20.000 — 1.5 100diethanolamine 24.419 diethyl maleate 20.000 — 6.5 1002-(methylamino)ethanol 20.000 diethyl maleate 22.933 — 6.5 100diethanolamine 24.138 diethyl succinate 20.000 0.110 6 100diethanolamine 26.250 dimethyl glutarate 20.000 0.120 6 100diethanolamine 26.923 DBE-9²⁾ 20.000 0.124 6 100 ethanolamine 15.640DBE-9²⁾ 20.000 0.124 6.5 100 2-(methylamino)ethanol 17.241 dimethyladipate 20.000 0.110 6.5 100 2-(methylamino)ethanol 19.231 DBE-9 20.0000.124 6.5 100 ethanolamine 15.062 dimethyl diglycolate 20.000 0.120 6.5100 diethanolamine 25.926 dimethyl diglycolate 20.000 0.120 6.5 1002-methylamino)ethanol 18.206 dimethyl diglycolate 19.662 0.100 6.25 100¹⁾grams of solid potassium hydroxide pellets (87% active); and ²⁾DBE-9is a commercial diester available from E. I. DuPont de Nemours,Wilmington, DE, and is a mixture of 66 wt % dimethyl succinate and 33 wt% dimethyl glutarate.

TABLE 3 Sample A¹⁾ L¹⁾ CR²⁾ Temp.³⁾ Time⁴⁾ CRC⁵⁾ 0.7 AUL 14 ——C(O)NHCH₂CH₂OH 0.01 165° C. 180 min. 30.0 21.8 15 — —C(O)N(CH₃)CH₂CH₂OH0.04 165° C. 120 min. 35.3 13.4 16 — —C(O)N(CH₂CH₂OH)₂ 0.04 165° C. 120min. 33.4 21.9 17 —CH₂— —C(O)NHCH₂CH₂OH 0.12 165° C. 120 min. 29.6 22.418 —CH₂— —C(O)N(CH₃)CH₂CH₂OH 0.10 165° C. 120 min. 29.8 22.6 19 —CH₂——C(O)N(CH₂CH₂OH)₂ 0.07 165° C. 120 min. 29.5 21.7 20 —(CH₂)₂——C(O)NHCH₂CH₂OH 0.05 165° C. 180 min. 31.4 24.3 21 —(CH₂)₂——C(O)N(CH₃)CH₂CH₂OH 0.07 165° C. 120 min. 29.8 24.5 22 —(CH₂)₂——C(O)N(CH₂CH₂OH)₂ 0.04 165° C.  90 min. 25.5 23.7 23 —(CH₂)₃——C(O)NHCH₂CH₂OH 0.07 165° C. 180 min. 30.0 24.4 24 —(CH₂)₃——C(O)N(CH₃)CH₂CH₂OH 0.04 165° C.  90 min. 26.7 25.2 25 —(CH₂)₃——C(O)N(CH₂CH₂OH)₂ 0.04 165° C.  90 min. 25.5 24.0 26 —(CH₂)₂₋₃—⁶⁾—C(O)NHCH₂CH₂OH 0.04 165° C.  90 min. 26.8 24.9 27 —(CH₂)₂₋₃ ⁶⁾—C(O)N(CH₃)CH₂CH₂OH 0.04 165° C.  90 min. 26.8 24.9 28 —(CH₂)₂₋₃ ⁶⁾—C(O)N(CH₂CH₂OH)₂ 0.04 165° C.  90 min. 25.1 24.0 29 —(CH₂)₄——C(O)NHCH₂CH₂OH 0.10 165° C. 120 min. 28.6 23.7 30 —(CH₂)₄—C(O)N(CH₃)CH₂CH₂OH 0.04 165° C. 120 min. 33.4 20.8 31 —(CH₂)₄——C(O)N(CH₂CH₂OH)₂ 0.04 165° C. 120 min. 29.6 22.0 32 —CH═CH——C(O)NHCH₂CH₂OH 0.04 165° C. 120 min. 33.2 11.9 33 —CH═CH——C(O)N(CH₃)CH₂CH₂OH 0.04 165° C. 120 min. 35.7 12.5 34 —CH═CH——C(O)N(CH₂CH₂OH)₂ 0.04 165° C. 120 min. 34.5 17.8 35 —CH₂OCH₂——C(O)NHCH₂CH₂OH 0.04 165° C.  60 min. 29.2 18.5 36 —CH₂OCH₂——C(O)N(CH₃)CH₂CH₂OH 0.04 165° C.  60 min. 28.8 19.9 37 —CH₂OCH₂——C(O)N(CH₂CH₂OH)₂ 0.04 165° C.  60 min. 28.2 21.3 38 —(CH₂)₂₋₃₋₄ ⁷⁾—C(O)N(CH₂CH₂OH)₂ 0.04 165° C.  90 min. 24.9 23.7 39 —(CH₂)₃₋₄ ⁸⁾—C(O)N(CH₂CH₂OH)₂ 0.04 165° C.  90 min. 25.9 23.6 Compara- Ethyleneglycol diglycidyl ether 0.04 165° C.  60 min. 30.5 24.0 tive 40 ¹⁾Component of the surface crosslinking compound of the formula L-A-L;²⁾CR is a weight ratio of surface crosslinking compound applied to thesurface of the SAP particles, based on SAP weight; ³⁾ Heatingtemperature; ⁴⁾Curing time; ⁵⁾CRC is retention capacity, in g 0.9% NaClper g of dry SAP, the CRC of control SAP particles lacking surfacecrosslinks is 34.3; ⁶⁾blend of 33% —(CH₂)₂— and 67% —(CH₂)₃—; ⁷⁾blend of20% —(CH₂)₂, 60% —(CH₂)₃, and 20% —(CH₂)₄—; and ⁸⁾blend of 75% —(CH₂)₃and 25% —(CH₂)₄—.

The data in Table 3 shows that surface crosslinking using an HAAprovides surface-treated SAP particles having a comparable AUL (Samples14-39) compared to SAP particles surface crosslinked with a diglycidylether (Comparative Sample 40). In addition, an HAA surface crosslinkerdid not adversely affect the CRC.

Preferred SAP particles of the present invention are surface crosslinkedwith an HAA, and have a 0.7 AUL of at least 15, and more preferably atleast 20. The preferred surface crosslinked SAP particles typically havea 0.7 AUL of about 15 to about 50. Preferred SAP particles of thepresent invention also have a CRC of less than 32.4, and more preferablyless than 31.5. Preferred SAP particles typically have a CRC of lessthan 32.4 to about 25. The properties exhibited by the HAAsurface-crosslinked SAP particles illustrate that HAA can be substitutedfor currently used surface-crosslinking agents, like EGDGE, and overcomedisadvantages associated with such crosslinking agents, e.g., colordegradation.

The surface crosslinked SAP particles of the present invention can beused as an absorbent in disposable diapers, sanitary napkins, andsimilar articles, and can be used in other applications, for example, adew formation inhibitor for building materials, a water-holding agentfor agriculture and horticulture, and a drying agent.

Surface-crosslinked SAP particles of the present invention haveadvantages over conventional absorbent particles. Thesurface-crosslinked SAP particles of the invention can be produced at alow cost by a simple method which involves mixing SAP particles with theHAA and heating. The resulting surface-crosslinked SAP particles areless susceptible to fish eye formation than conventional absorbentresins and, therefore, exhibit a high rate of liquid absorption Thepresent surface-crosslinked SAP particles also are white to off-white incolor.

Obviously, many modifications and variations of the invention ashereinbefore set forth can be made without departing from the spirit andscope thereof, and, therefore, only such limitations should be imposedas are indicated by the appended claims.

What is claimed is:
 1. Superabsorbent polymer particles comprising 100parts by weight of a water-absorbing resin and about 0.001 to about 10parts by weight of a hydroxyalkylamide, wherein the hydroxyalkylamide ispresent at surfaces of the water-absorbing resin and crosslinks polymerchains at the surfaces of the water-absorbing resin.
 2. The particles ofclaim 1 wherein the particles contain about 0.01 to about 4 parts byweight of the hydroxyalkylamide, per 100 parts by weight of thewater-absorbing resin.
 3. The particles of claim 1 wherein the particlescontain about 0.4 to about 2 parts by weight of the hydroxyalkylamide,per 100 parts by weight of the water-absorbing resin.
 4. The particlesof claim 1 wherein the hydroxyalkylamide has the structure

wherein A is a bond, hydrogen, a monovalent or polyvalent organicradical selected from the group consisting of a saturated or unsaturatedalkyl radical containing 1 to 60 carbon atoms, aryl, tri-C₁₋₄alkyleneamine, and an unsaturated radical containing one or moreethylenic groups; R¹, selected independently, are hydrogen, straight orbranched chain C₁₋₅ alkyl, or straight or branched chain C₁₋₅hydroxyalkyl; R², selected independently, are radicals selected from thegroup consisting of hydrogen and straight or branched C₁₋₅ alkyl, or theR² radicals are joined to form, together with carbon atoms, a cycloalkylring; p and p′, independently, are an integer 1 to 4; n is an integerhaving a value of 1 or 2, and n′ is an integer having a value of 0 to 2;or when n′ is 0, a polymer or copolymer, wherein n is greater than 1formed from the hydroxyalkylamide when A is an unsaturated radical. 5.The particles of claim 4 wherein the hydroxyalkylamide has the structure

wherein R¹ is H or C₁₋₅ hydroxyalkyl, m is 0-8, and one of the R²radicals on the beta carbon is H and the other is H or a C₁₋₅ alkyl, andq and q′, independently, are an integer 1 to
 3. 6. The particles ofclaim 4 wherein the hydroxyalkylamide has the structure

wherein both R² groups are H or both R² groups are —CH₃.
 7. Theparticles of claim 1 wherein the hydroxyalkylamide has the structure

where R³ is a divalent radical selected from the group consisting of analkylene radical containing 1 to 4 carbon atoms and arylene.
 8. Theparticles of claim 1 wherein the hydroxyalkylamide is selected from thegroup consisting of bis[N,N-di(β-hydroxyethyl)]adipamide,bis[N,N-di(β-hydroxypropyl)]succinamide,bis[N,N-di(β-hydroxyethyl)]azelamide,bis[N-N-di(β-hydroxypropyl)]adipamide,bis[N-methyl-N-(β-hydroxyethyl)]oxamide, and mixtures thereof.
 9. Theparticles of claim 1 wherein the hydroxyalkylamide has the structure


10. The particles of claim 1 wherein the hydroxyalkylamide has thestructure


11. The particles of claim 1 the hydroxyalkylamide has a structureL—A—L, wherein A is selected from the group consisting of (CH₂)_(n),CH═CH, and CH₂OCH₂, L, independently, is selected from the groupconsisting of —C(═O)N(CH₃)CH₂CH₂OH, —C(═O)NHCH₂CH₂OH, and—C(═O)N(CH₂CH₂OH)₂, and n is 0, 1, 2, 3, or
 4. 12. The particles ofclaim 11 wherein the hydroxyalkylamide is selected from the groupconsisting of bis[N-methyl-N-(β-hydroxyethyl)]succinamide,bis[N-methyl-N-(β-hydroxyethyl)]glutaramide,bis[N-methyl-N-(β-hydroxyethyl)]succinamide/glutaramide,bis[N,N-(dihydroxyethyl)]succinamide,bis[N,N-(dihydroxyethyl)]glutaramide,bis[N,N-(dihydroxyethyl)]succinamide/glutaramide,bis[N,N-(dihydroxyethyl)]succinamide/glutaramide/adipamide,bis[N,N-(dihydroxyethyl)]glutaramide/adipamide, and mixtures thereof.13. The particles of claim 11 wherein the hydroxyalkylamide comprises areaction product of a reaction between (a) ethanolamine, diethanolamine,2-(methylamino)ethanol, and mixtures thereof, and (b) a diethyl or adimethyl ester of succinic acid, glutaric acid, malenic acid, oxalicacid, adipic acid, maleic acid, and mixtures thereof.
 14. The particlesof claim 1 wherein the water-absorbing resin comprises an acidicwater-absorbing resin.
 15. The particles of claim 14 wherein the acidicwater-absorbing resin is a neutralized, lightly crosslinked acrylic-typeresin containing at least 10% acidic monomer units.
 16. The particles ofclaim 15 wherein the acidic monomer units have a carboxylate, sulfonate,sulfate, or phosphate group.
 17. The particles of claim 14 wherein theacidic monomer units are selected from the group consisting of acidicwater-absorbing resin include acrylic acid, methacrylic acid, ethacrylicacid, α-chloroacrylic acid, α-cyanoacrylic acid, β-methylacrylic acid,α-phenylacrylic acid, β-acryloxypropionic acid, sorbic acid,α-chlorosorbic acid, angelic acid, cinnamic acid, p-chlorocinnamic acid,β-stearylacrylic acid, itaconic acid, citraconic acid, mesaconic acid,glutaconic acid, aconitic acid, maleic acid, fumaric acid,tricarboxyethylene, 2-methyl-2-butene dicarboxylic acid, maleamic acid,N-phenyl maleamide, maleamide, maleic anhydride, fumaric anhydride,itaconic anhydride, citraconic anhydride, mesaconic anhydride, methylitaconic anhydride, ethyl maleic anhydride, diethylmaleate,methylmaleate, maleic anhydride, vinylsulfonic acid, allyl sulfonicacid, vinyl toluene sulfonic acid, styrene sulfonic acid, an acrylicsulfonic acid, a methacrylic sulfonic acid, sulfoethyl acrylate,sulfoethyl methacrylate, sulfopropyl acrylate, 2-vinyl-4-ethylbenzene,2-allylbenzene sulfonic acid, 1-phenylethylene sulfonic acid,sulfopropyl methacrylate, 2-hydroxy-3-methacryloxypropyl sulfonic acid,2-acrylamide-2-methylpropane sulfonic acid, sulfated polyvinylalcohol,sulfated hydroxyethyl acrylate, sulfated hydroxypropyl methacrylate,methacryloxyethyl phosphate, and mixtures thereof.
 18. The particles ofclaim 14 wherein the acidic water-absorbing resin is selected from thegroup consisting of a starch-acrylic acid graft copolymers, a saponifiedvinyl acetate-acrylic ester copolymer, a hydrolyzed acrylonitrilecopolymer, a hydrolyzed acrylamide copolymer, an ethylene-maleicanhydride copolymer, an isobutylene-maleic anhydride copolymer,poly(vinylsulfonic acid), poly(vinylphosphonic acid),poly(vinylphosphoric acid), poly(vinylsulfuric acid), sulfonatedpolystyrene, poly(aspartic acid), poly(lactic acid), and mixturesthereof, neutralized 20 to 100 mole percent with a base.
 19. Theparticles of claim 1 wherein the water-absorbing resin is polyacrylicacid neutralized 50 to 100 mole percent.
 20. The particles of claim 1wherein the water-absorbing resin comprises a basic water-absorbingresin.
 21. The particles of claim 20 wherein the basic water-absorbingresin is a neutralized, lightly crosslinked resin containing at least10% basic monomer units.
 22. The particles of claim 20 wherein the basicwater-absorbing resin is selected from the group consisting of apoly(vinylamine), a poly(alkylaminoalkyl (meth)acrylamide, apolyethylenimine, a poly(allylamine), a poly(allylguanidine), apoly(dimethylallylammonium hydroxide), a quaternized polystyrene, aguanidine-modified polystyrene, a quaternized poly(meth)acrylamide orester analog thereof, a poly(vinylguanidine), and mixtures thereof. 23.The particles of claim 1 wherein the water-absorbing resin comprises amixture of an acidic water-absorbing resin and a basic water-absorbingresin.
 24. The particles of claim 1 wherein the water-absorbing resincomprises multicomponent superabsorbent polymer particles.
 25. Theparticles of claim 1 having an absorption under a load of 0.7 psi afterone hour of at least 20 grams of 0.9% saline per gram of particles. 26.The particles of claim 1 having an AUL at 0.7 psi of greater than 15 anda CRC of less than 32.4.
 27. The particles of claim 1 having an AUL at0.7 psi or greater than
 20. 28. The particles of claim 27 having a CRCof less than 31.5.
 29. Surface crosslinked superabsorbent polymerparticles obtained by mixing 100 parts, by weight, of a superabsorbentpolymer with about 0.001 to about 10 parts, by weight, of ahydroxyalkylamide to form surface-treated superabsorbent polymerparticles, then heating the surface-treated superabsorbent particles atabout 90° C. to about 170° C. for about 60 to about 180 minutes to formsurface crosslinks on the surface-treated superabsorbent polymerparticles.
 30. A method of preparing surface crosslinked superabsorbentpolymer particles comprising: (a) providing 100 parts by weight ofsuperabsorbent polymer particles; (b) forming a solution comprisingabout 0.5% to about 50% by weight of a hydroxyalkylamide in a solventcapable of solubilizing the hydroxyalkylamide; (c) applying the solutionof (b) to surfaces of (a) to provide surface-treated superabsorbentpolymer particles having about 0.001 to about 10 parts, by weight, ofthe hydroxyalkylamide per 100 parts, by weight, of superabsorbentpolymer particles in the vicinity of the surfaces of the superabsorbentpolymer particles; and (d) heating the surface-treated superabsorbentpolymer particles at about 90° C. to about 170° C. for about 60 to about180 minutes to form surface crosslinks in the vicinity of the surface ofthe superabsorbent polymer particles.
 31. The method of claim 30 whereinstep (c) is performed prior to step (d).
 32. The method of claim 30wherein steps (c) and (d) are performed simultaneously.
 33. The methodof claim 30 wherein the hydroxyalkylamide solution of step (b) furthercomprises a second surface crosslinking agent selected from the groupconsisting of a diol, a triol, a polyol, a divalent metal, a trivalentmetal, a diglycidyl ether, a diamine, a halohydrin, a polyisocyanate, adihaloalkane, a polyfunctional aziridine compound, a dialdehyde, adisulfonate ester, a diester, a multifunctional acid halide, an organictitanate, a melamine resin, a hydroxymethyl urea, and mixtures thereof.34. The method of claim 33 wherein the second surface crosslinking agentcomprises ethylene glycol, propylene glycol, 1,3-butanediol,1,4-butanediol, ethylene glycol diglycidyl ether, and mixtures thereof.35. The method of claim 30 wherein the hydroxyalkylamide solution ofstep (b) further comprises a second surface crosslinking agent capableof forming surface crosslinks on the superabsorbent polymer particles ata temperature of about 90° C. to about 160° C.
 36. A method of preparingsurface crosslinked superabsorbent polymer particles comprising: (a)polymerizing a mixture containing (i) unsaturated polymerizable monomershaving acid groups or basic groups, and (ii) a polyfunctionalcrosslinking agent, dissolved in (iii) a solvent comprising water toform a superabsorbent polymer hydrogel; (b) adding a sufficient amountof a hydroxyalkylamide to the superabsorbent polymer hydrogel to provideabout 0.001 to about 10 parts, by weight, of the β-hydroxyalkylamide per100 parts, by weight, of the superabsorbent polymer; and (c) heating theproduct of step (b) at about 90° C. to about 170° C. to dry thesuperabsorbent polymer hydrogel, form superabsorbent polymer particles,and form crosslinks on the surface of the superabsorbent polymerparticles.
 37. Surface crosslinked superabsorbent polymers prepared bythe method of claim
 36. 38. An article comprising the superabsorbentparticles of claim
 1. 39. The article of claim 38 wherein the article isa diaper or a catamenial device.